CN1383436A - Epoxy resin compsn. and laminate using same - Google Patents

Epoxy resin compsn. and laminate using same Download PDF

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Publication number
CN1383436A
CN1383436A CN01801664A CN01801664A CN1383436A CN 1383436 A CN1383436 A CN 1383436A CN 01801664 A CN01801664 A CN 01801664A CN 01801664 A CN01801664 A CN 01801664A CN 1383436 A CN1383436 A CN 1383436A
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Prior art keywords
epoxy resin
copper film
stock
composition
acid
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Granted
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CN01801664A
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CN1150244C (en
Inventor
金英植
金贤哲
申东洛
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LG Corp
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LG Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2904—Staple length fiber
    • Y10T428/2907—Staple length fiber with coating or impregnation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2916—Rod, strand, filament or fiber including boron or compound thereof [not as steel]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2938—Coating on discrete and individual rods, strands or filaments

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Epoxy Resins (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a nonflammable epoxy resin composition for using a thin copper film laminate, which is applied to a printed circuit board (PCB), and using the same. The present invention provides for nonflammable epoxy resin composition for using a thin copper film laminate, comprising bisphenol A-type epoxy resin, multifunctional epoxy resin, an imidazole-based curing catalyst, and a curing retarder. As described above, since the ring-open of the epoxy group is prompted by an imidazole catalyst, without the use of dicyandiamide, epoxy polymer reaction occurs due to the chain-reaction of epoxy group, and the glass-transition temperature is 170 DEG C or greater, the nonflammable epoxy resin composition for using a thin copper film of the present invention has a strong heat-resistance, lower dielectric constant, controllable gelation time, and does not require the use of non-harmful catalysts to the human body.

Description

Composition epoxy resin and laminate thereof
The mutual reference of related application
The application No.2000-0031965 that the application submitted to Korea S industrial property office based on June 10th, 2000, in this content of quoting it as a reference.
Background of invention
(a) invention field
The present invention relates to be used to use the composition epoxy resin of nonflammable thin copper film layer rolled-up stock, said composition can be used for printed-wiring board (PWB) (PCB), and available its prepared layer rolled-up stock.
(b) description of Related Art
In conventional composition epoxy resin, generally usually use amido solidifying agent and curing catalyst, and the dual functional and polyfunctional Resins, epoxy of bromination is as essential substance, the normal brominated epoxy resin that uses obtains noninflammability, and uses trifunctional or polyfunctional epoxy resin to improve thermotolerance and physical strength.But, since only when using Resins, epoxy curing reaction be not easy to take place, so by adding solidifying agent in Resins, epoxy, and the activation epoxide group makes Resins, epoxy obtain solidifying.
At present, use Dyhard RU 100 as solidifying agent usually, yet owing to only use under the situation of Dyhard RU 100, the speed of reaction of Dyhard RU 100 and Resins, epoxy is very slow, therefore general adding imidazoles is as curing catalysts.U.S.Pat.No.5308895, No.5508328, No.5620789 and No.5721323 show: add boric acid as curing inhibitors, purpose is in order to improve second-order transition temperature, thereby has improved degree of cure by the control solidification rate and owing to increase cured density.Yet, use Dyhard RU 100 as solidifying agent, second-order transition temperature (Tg) is 140 ℃～160 ℃.
Because the coordinate bond of boric acid and imidazoles prevents the imidazoles cured epoxy resin at low temperatures, have the stability of improvement under the epoxy resin at room temp, and the curing of dative bond inhibition Resins, epoxy at low temperatures.Usually, boric acid and imidazoles decomposed to each other in time more than 120 ℃ or 120 ℃, and the imidazoles that take place to decompose improved the speed of response of Dyhard RU 100, and because the epoxide group open loop has been quickened in the raising of speed of response.Therefore, along with the raising of epoxy resin cure speed, second-order transition temperature raises then.
But, use Dyhard RU 100 to require organic solvent such as N, dinethylformamide (DMF) and N-methyl 2-Pyrrolidone, they all are deleterious to human body, because the solubleness of Dyhard RU 100, and the shelf characteric that will aspire for stability, because Dyhard RU 100 low temperature precipitates down.And the thermotolerance of Resins, epoxy and Dyhard RU 100 is limited in more than 250 ℃ or 250 ℃, because Dyhard RU 100 is originally in more than 200 ℃ or 200 ℃ cracking taking place.In addition, cause the specific inductivity of Resins, epoxy to improve owing to add Dyhard RU 100.
Correspondingly, when not using the Dyhard RU 100 imidazoles to promote under the situation of Resins, epoxy open loop, and by the chain transfer reaction of epoxide group the epoxy polymer reaction has taken place, can produce second-order transition temperature and be 170 ℃ or greater than 170 ℃ and have an improved stable on heating thin copper film layer rolled-up stock, because polymer bonds becomes stronger, make cured density obtain increasing.In addition, thin copper film layer rolled-up stock has lower specific inductivity than tradition stratum rolled-up stock.But, the composition epoxy resin of thin copper film layer rolled-up stock does not also appear being used for as mentioned above.
Be used to use the nonflammable Resins, epoxy thermotolerance of thin copper film layer rolled-up stock to represent, and to have second-order transition temperature be that 120 ℃～150 ℃ Resins, epoxy are often used as the product into FR-4 with second-order transition temperature.Along with the rising of second-order transition temperature because the thermotolerance of the high cured density Resins, epoxy of Resins, epoxy also increases since thermal expansion is less high temperature under have suitable size because fine and close molecular structure has lower water-absorbent.Therefore, can produce thin copper film layer rolled-up stock, for the lower fluoropolymer resin of second-order transition temperature.In order to improve second-order transition temperature, adopted some method, wherein added and had trifunctional or multi-functional Resins, epoxy, added novolak, blend BT resin or polymeric amide.
Summary of the invention
The consideration problems of the prior art have been carried out the present invention, and an object of the present invention is to provide the nonflammable composition epoxy resin that is used for thin copper film layer rolled-up stock, therefore obtain improved thermotolerance more than 170 ℃ or 170 ℃ owing to second-order transition temperature is brought up to, said composition is to promote the epoxy polymer reaction of epoxide group open loop to make by imidazoles under the situation of not using Dyhard RU 100.
Another object of the present invention provides has nonflammable composition epoxy resin low-k, that be used for the copper film layer rolled-up stock, and with its preparation laminate.
Another object of the present invention provides the nonflammable composition epoxy resin that is used for the copper film layer rolled-up stock, and said composition is to prepare under situation about not using the health hazardous solvent, and the laminate with its preparation is provided.
Thereby another object of the present invention provides the nonflammable composition epoxy resin that has controlled gelation time by gate ring epoxy resins solidification rate, and with its preparation laminate.
Be used to use the nonflammable composition epoxy resin of thin copper film layer rolled-up stock to comprise in order to reach these purposes, to the invention provides:
A) bromo bisphenol A-type bifunctional epoxy resin;
B) polyfunctional epoxy resin;
C) imidazolyl curing catalysts; With
D) curing inhibitors.
The present invention also provides thin copper film layer rolled-up stock, and it comprises with one or more epoxy resin impregnated
The glass layer rolled-up stock of crossing, and be positioned at thin copper film on the glass layer rolled-up stock skin,
Wherein tightly link together between glass layer rolled-up stock and the thin copper film.
Detailed Description Of The Invention
In the following detailed description, the contriver is only to enumerate the method for best mode, represents and described the preferred embodiments of the invention.Should be realized that, under the situation that does not deviate from all the elements of the present invention, can make amendment to the present invention aspect conspicuous various.Therefore, description should be thought the elaboration of essential aspect, and not limited.
Composition epoxy resin of the present invention is used to the thin copper film layer rolled-up stock of nonflammable, impregnated glass layer rolled-up stock, owing to be the open loop of epoxide group, therefore is cured by imidazole catalyst, has replaced conventional Dyhard RU 100.
Bisphenol A type epoxy resin of the present invention comprises bromine, and preferred bromine content is 15 weight %～55 weight %, and bromine can make thin copper film layer rolled-up stock have noninflammability, and the equivalence ratio of Resins, epoxy is preferably 300～1500.
In addition, polyfunctional epoxy resin of the present invention contains 3 or a plurality of epoxy-functional at least in each molecule, i.e. trifunctional and four-functional group and as the phenolic novolac of general polyfunctional epoxy resin.Usually, along with the increase of functional group's number, the second-order transition temperature of Resins, epoxy is also along with raising.
In solidification process, Resins, epoxy needs solidifying agent, and the amido solidifying agent is used as conventional solidifying agent, and it is the solubleness of organic solvent that individual problem is arranged, and requires abstruse method.So replenishing as conventional solidifying agent, solidifying agent of the present invention comprises imidazoles, as 1-Methylimidazole, glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-cyclohexyl-4-methylimidazole, 4-butyl-5-ethyl imidazol(e), 2-methyl-5-ethyl imidazol(e), 2-octyl group-4-hexyl imidazoles, 2,5-chloro-4-ethyl imidazol(e) and 2-butoxy-4-allyl imidazole, and imdazole derivatives.
The content of imidazoles is preferably 0.1～20 weight part, with respect to 100 parts by weight of epoxy resin (gross weight of bifunctional epoxy resin and polyfunctional epoxy resin), and more preferably with 1～5 weight part.
Use imidazoles to improve epoxy resin gel speed, and Resins, epoxy is not easy molding, because gel time is shorter than 200 seconds even shorter.Therefore the purpose of using curing inhibitors is in order to control gel speed and gel time to be brought up to more than 200 seconds or 200 seconds, and curing inhibitors is put into mould easily.Curing inhibitors comprises boric acid, Whitfield's ointment, hydrochloric acid, sulfuric acid, oxalic acid, terephthalic acid, m-phthalic acid, phosphoric acid, lactic acid, phenyl-boron dihydroxide and toluene sulfuric acid, and the curing inhibitors amount of using preferably with every mole of imidazoles equivalent weight serve as the basis every mole 0.1～10 equivalent, more preferably every mole of imidazoles 0.5～5 equivalent.
Although the Resins, epoxy among the present invention can use with a small amount of polyfunctional epoxy resin, but it is 170 ℃ or greater than 170 ℃ that the present invention has second-order transition temperature, because can be by adding solidification rate and the cured density that come the gate ring epoxy resins respectively as the imidazoles of catalyzer and curing inhibitors.Therefore, can make and have strong stable on heating nonflammable thin copper film layer rolled-up stock.In addition, the use imidazoles can not need to use the amido solidifying agent as Dyhard RU 100, and it has lower solubleness with respect to organic solvent, and performance is undesirable under the high temperature, also can harmful solvent such as the DMF of unnecessary use in solidification process.Therefore, this method is an ideal aspect environmental protection, and specific inductivity can reduce.
Describe the while of the present invention in detail with reference to preferred embodiment, those skilled in the art will appreciate that, can make various modifications and replacement not deviating from the present invention under the situation of aim that claims propose and scope.
(embodiment)
Embodiment 1
(preparation of composition epoxy resin)
According to the composition of table 1 expression, composition epoxy resin obtains preparation.
At first, the 2-phenylimidazole of 2.0g and the boric acid of 0.85g are joined in the 500ml beaker, and add 25g methylcyclohexane (MCS: the glycol monomethyl methyl ether) mixture is dissolved fully therein.
Is 450 bifunctional epoxy resin with 125g bromo bisphenol-A type Resins, epoxy (LG Chem preparation LER-1222M80) as equivalent weight, joins in the solution, and stirred solution is up to mixing fully.
In addition, (Shell company makes, and EPON1030), is dissolved in fully among the 50gMCS, joins in the solution back and stirs up to mixing fully with the four sense Resins, epoxy of 50g.
With temperature is the gel time of 170 ℃ hot plate measurement composition epoxy resin, and gel time is 210 seconds.
(manufacturing of thin copper film layer rolled-up stock)
The composition epoxy resin of preparation is with glass fibre (Nittobo company, production number No.7628) dipping, and is 43 weight % with epoxy resin content in the pre-impregnated article of hot blast dried preparation.
8 sheet glass fiber pre-impregnated articles are carried out lamination, with the copper film of 35 μ m further be laminated to the top of pre-impregnated article and below, and zone of heating press mold and at 185 ℃, 40kg/cm 3Under pushed 90 minutes, finally preparing thickness then is the copper film layer rolled-up stock of 1.6mm.
(test of thin copper film layer rolled-up stock)
To approach the surface removal of copper film from thin copper film layer rolled-up stock with etching method, the second-order transition temperature of measuring film with DSC (differential scanning calorimeter) is 177 ℃.
It is that the sample of 1.6mm is positioned over and measures anti-lead in the plumbous stove that sample is cut into 5cm * 5cm size, thickness, and the tolerance time of measure sample.
Measure thermotolerance in baking oven, the sample that will cut into 5cm * 5cm size, thickness and be 1.6mm is positioned over to have in 270 ℃ of homothermic baking ovens, and the tolerance time of measure sample.
In order to measure the change in dielectric constant of the product of removing Dyhard RU 100, make thin copper film layer rolled-up stock with above-described same mode, glass fibre is converted into product No.2116, and to make thickness be the product of 0.5mm, measures the specific inductivity of products at last according to JIS C 6481.The results are shown in Table 1.
Comparative example 1
(preparation of composition epoxy resin under the situation of use Dyhard RU 100)
Prepare a kind of composition epoxy resin with Dyhard RU 100 as solidifying agent, said composition is generally used for preparing FR-4, according to composition shown in the table 1.
2-phenylimidazole and the 5.60g Dyhard RU 100 of 2.0g are joined in the 500ml beaker, and adding 45g methylcyclohexane (MCS: the glycol monomethyl methyl ether) and behind the 10gDMF mixture is dissolved fully subsequently.
With 125g bromo bisphenol-A type Resins, epoxy (LG Chem preparation LER-1222M80) as
In addition, (Shell company makes, and EPON1030), is dissolved in fully among the 50gMCS, joins in the solution back and stirs up to mixing fully with the four sense Resins, epoxy of 50g.
With the gel time of 170 ℃ hot plates measurement composition epoxy resins, gel time is 250 seconds.
Make the copper film layer rolled-up stock that thickness is 1.6mm according to mode same among the embodiment, and measure second-order transition temperature, anti-lead, and the thermotolerance of thin copper film layer rolled-up stock in baking oven.
In addition, according to the same manner of embodiment 1, making thickness is product and the Measuring Dielectric Constant of 0.5mm, and test result is represented with table 1.
Comparative example 2 and 3
According to the same manner of embodiment 1, in the baking oven of conventional FR-4 and FR-5, measure second-order transition temperature, anti-lead and thermotolerance, and test result is listed in the table 1.
Table 1
Kind Embodiment 1 Comparative example 1 Comparative example 2 (FR-4) Comparative example 3 (FR-5)
Composition epoxy resin (phr) Bifunctional epoxy resin (LER1222M80) ????125 ????125 ????- ????-
Four sense Resins, epoxy (EPON-1030) ????50 ????50
Imidazoles (2-phenylimidazole) ????2.0 ????0.2
Dyhard RU 100 ????- ????5.60
Curing inhibitors (boric acid) ????0.85 ????-
Performance Gel time (second) ????210 ????250 ????- ????-
Second-order transition temperature (℃) ????177 ????158 ????125 ????175
Anti-lead (second) More than 900 or 900 ????305 ????300 ????618
Thermotolerance in the baking oven (second) More than 1200 or 1200 ????605 ????585 ????715
Specific inductivity ????4.4～4.5 ????4.7～4.8 ????- ????-
Embodiment 2～5
As shown in table 2 below, the content of imidazoles and curing inhibitors changes, and according to the same manner in the foregoing description 1, preparation composition epoxy resin and thin copper film layer rolled-up stock.Performance is listed in the table 2.
Table 2
Kind Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Composition epoxy resin (phr) Bifunctional epoxy resin (LER1222M80) ????125 ????125 ????125 ????125
Four sense Resins, epoxy (EPON-1031) ????50 ????50 ????50 ????50
Imidazoles (2-phenylimidazole) ????1.0 ????1.5 ????2.0 ????2.5
Curing inhibitors (boric acid) ????0.44 ????0.64 ????0.85 ????1.05
Performance Gel time (second) ????366 ????230 ????210 ????149
Second-order transition temperature (℃) ????164 ????172 ????180 ????185
According to test result, along with imidazoles content increases, gel time descends, and this is that still, behind the molding, the second-order transition temperature of thin copper film layer rolled-up stock is owing to the increase of cured density improves owing to increased the gel time of Resins, epoxy.
Embodiment 6～9
As shown in table 3 below, change imidazoles content, and according to the same manner of the foregoing description 1, the preparation composition epoxy resin, and make thin copper film layer rolled-up stock.Performance is listed in the table 3.
Table 3
Kind Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9
Composition epoxy resin (phr) Bifunctional epoxy resin (LER1222M80) ????125 ????125 ????125 ????125
Four sense Resins, epoxy (EPON-1031) ????50 ????50 ????50 ????50
Imidazoles (2-phenylimidazole) ????2.0 ????2.0 ????2.0 ????2.0
Curing inhibitors (boric acid) ????0.64 ????0.83 ????1.09 ????1.30
Performance Gel time (second) ????230 ????250 ????250 ????205
Second-order transition temperature (℃) ????172 ????175 ????176 ????173
The imidazoles and the boric acid content that are used separately as solidifying agent and curing inhibitors by control are measured the ideal gel time, and second-order transition temperature is brought up to 170 ℃ or be higher than 170 ℃.
As described above, owing to promoted the open loop of epoxide group with imidazole catalyst, under the situation of not using Dyhard RU 100, because the chain reaction of epoxide group, make the epoxy polymer reaction has taken place, and second-order transition temperature is 170 ℃ or greater than 170 ℃, uses the nonflammable composition epoxy resin of the thin copper film layer rolled-up stock of the present invention to have strong thermotolerance, than low-k, controlled gel time, and do not require and use harmless catalyzer.

Claims (8)

1, be used to use a kind of nonflammable composition epoxy resin of thin copper film layer rolled-up stock, comprise:
A) bromo bisphenol A-type bifunctional epoxy resin;
B) polyfunctional epoxy resin;
C) imidazolyl catalyzer; With
D) curing inhibitors.
2, according to the composition epoxy resin of right 1, wherein the bromine content that contains among bifunctional epoxy resin a) is 15～55 weight %.
3, polyfunctional epoxy resin according to the composition epoxy resin of right 1, b wherein) is selected from trifunctional epoxy resin, four sense Resins, epoxy, phenolic novolac and their mixture.
4, according to the composition epoxy resin of right 1, wherein be used for c) the imidazole catalyst of curing reaction be selected from 1-Methylimidazole, glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-cyclohexyl-4-methylimidazole, 4-butyl-5-ethyl imidazol(e), 2-methyl-5-ethyl imidazol(e), 2-octyl group-4-hexyl imidazoles, 2,5-chloro-4-ethyl imidazol(e), 2-butoxy-4-allyl imidazole, and their mixture.
5, imidazole catalyst content according to the composition epoxy resin of right 1, c wherein) is 0.1～20 weight part, with respect to for 100 parts by weight of epoxy resin.
6, curing inhibitors according to the composition epoxy resin of right 1, d wherein) is selected from boric acid, Whitfield's ointment, hydrochloric acid, sulfuric acid, oxalic acid, terephthalic acid, m-phthalic acid, phosphoric acid, lactic acid, phenyl-boron dihydroxide and toluene sulfuric acid, and their composition.
7, curing inhibitors content according to the composition epoxy resin of right 1, d wherein) is 0.1～10 equivalent weight, with respect to for the imidazole catalyst equivalent.
8, a kind of thin copper film layer rolled-up stock, comprise glass layer rolled-up stock with one or more epoxy resin impregnated mistakes, with the copper film that is positioned on the glass layer rolled-up stock skin, wherein glass layer rolled-up stock and copper film link together by heating and extruding, and wherein composition epoxy resin comprises:
A) bromo bisphenol A-type bifunctional epoxy resin;
B) polyfunctional epoxy resin;
C) imidazolyl curing catalysts; With
D) curing inhibitors.
CNB018016642A 2000-06-10 2001-06-08 Epoxy resin compsn. and laminate using same Expired - Fee Related CN1150244C (en)

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TWI259187B (en) 2006-08-01
JP2004503632A (en) 2004-02-05
US6703124B2 (en) 2004-03-09
US20030054146A1 (en) 2003-03-20
JP3958209B2 (en) 2007-08-15
KR20010111361A (en) 2001-12-17
CN1150244C (en) 2004-05-19
WO2001096440A1 (en) 2001-12-20

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